Acid chloride solution process

V. H. Aprahamian and D. G. Demopoulos, The Solution Chemistry and Solvent Extraction Behaviour of copper, iron, nickel, zinc, lead, tin, Ag, arsenic, antimony, bismuth, selenium and tellurium in Acid Chloride Solutions Reviewed from the Standpoint of PGM Refining, Mineral Processing and Extractive Metallurgy Review, Vol. 14, p. 143,1995. 

Fluang [246] investigated the SCC of AISI 321 stainless steel in acidic chloride solutions by the SSRT technique and fracture mechanics. It was found that the cleavage fracture characterizes the fracture surface. The active dissolution mechanism controls the SCC of AISI 321 stainless steel in acidic chloride solutions and can be inhibited by using KI. The inhibition effect of KI on the SCC is due to inhibition of the anodic reaction of the corrosion process. 

To a tail-form beaker is added a solution of 3.0 ml (0.014 mole) of sebacoyl chloride dissolved in 100 ml of distilled tetrachloroeth-ylene. Over this acid chloride solution is carefully poured a solution of 4.4 gm (0.038 mole) of hexamethylenediamine (see Note) dissolved in 50 ml of water. The polyamide film which begins to form at the interface of these two solutions is grasped with tweezers or a glass rod and slowly pulled out of the beaker in a continuous fashion. The process stops when one of the reactants becomes depleted. The resulting rope -like polymer is washed with 50% aqueous ethanol or acetone, dried, and weighed to afford 3.16-3.56 gm (80-90%) yields of polyamide, 7i h = 0.4 to 1.8 (w-cresol, 0.5% cone, at 25°C), m.p. 215°C (soluble in formic acid). 

Nylon 6 and 6/6 possess the maximum stiffness, strength, and heat resistance of all the types of nylon. Type 6/6 has a higher melt temperature, whereas type 6 has a higher impact resistance and better processibility. At a sacrifice in stiffness and heat resistance, the higher analogs of nylon are useful primarily for improved chemical resistance in certain environments (acids, bases, and zinc chloride solutions) and for lower moisture absorption. 

Most cellulose acetate is manufactured by a solution process, ie, the cellulose acetate dissolves as it is produced. The cellulose is acetylated with acetic anhydride acetic acid is the solvent and sulfuric acid the catalyst. The latter can be present at 10—15 wt % based on cellulose (high catalyst process) or at ca 7 wt % (low catalyst process). In the second most common process, the solvent process, methylene chloride replaces the acetic acid as solvent, and perchloric acid is frequentiy the catalyst. There is also a seldom used heterogeneous process that employs an organic solvent as the medium, and the cellulose acetate produced never dissolves. More detailed information on these processes can be found in Reference 28. 

Re OPe . The final step in the chemical processing of rare earths depends on the intended use of the product. Rare-earth chlorides, usually electrolytically reduced to the metallic form for use in metallurgy, are obtained by crystallisation of aqueous chloride solutions. Rare-earth fluorides, used for electrolytic or metaHothermic reduction, are obtained by precipitation with hydrofluoric acid. Rare-earth oxides are obtained by firing hydroxides, carbonates or oxalates, first precipitated from the aqueous solution, at 900°C. 

Interfdci l Composite Membra.nes, A method of making asymmetric membranes involving interfacial polymerization was developed in the 1960s. This technique was used to produce reverse osmosis membranes with dramatically improved salt rejections and water fluxes compared to those prepared by the Loeb-Sourirajan process (28). In the interfacial polymerization method, an aqueous solution of a reactive prepolymer, such as polyamine, is first deposited in the pores of a microporous support membrane, typically a polysulfone ultrafUtration membrane. The amine-loaded support is then immersed in a water-immiscible solvent solution containing a reactant, for example, a diacid chloride in hexane. The amine and acid chloride then react at the interface of the two solutions to form a densely cross-linked, extremely thin membrane layer. This preparation method is shown schematically in Figure 15. The first membrane made was based on polyethylenimine cross-linked with toluene-2,4-diisocyanate (28). The process was later refined at FilmTec Corporation (29,30) and at UOP (31) in the United States, and at Nitto (32) in Japan. 

Phosgene addition is continued until all the phenoHc groups are converted to carbonate functionahties. Some hydrolysis of phosgene to sodium carbonate occurs incidentally. When the reaction is complete, the methylene chloride solution of polymer is washed first with acid to remove residual base and amine, then with water. To complete the process, the aqueous sodium chloride stream can be reclaimed in a chlor-alkah plant, ultimately regenerating phosgene. Many variations of this polycarbonate process have been patented, including use of many different types of catalysts, continuous or semicontinuous processes, methods which rely on formation of bischloroformate oligomers followed by polycondensation, etc. 

The ammonium sulfate and sodium chloride are simultaneously dissolved, preferably ia a heel of ammonium chloride solution. The sodium chloride is typically ia excess of about 5%. The pasty mixture is kept hot and agitated vigorously. When the mixture is separated by vacuum filtration, the filter and all connections are heated to avoid cmst formation. The crystalline sodium sulfate is washed to remove essentially all of the ammonium chloride and the washings recycled to the process. The ammonium chloride filtrate is transferred to acid resistant crystallising pans, concentrated, and cooled to effect crystallisation. The crystalline NH Cl is washed with water to remove sulfate and dried to yield a product of high purity. No attempt is made to recover ammonium chloride remaining ia solution. The mother Hquor remaining after crystallisation is reused as a heel. 

Two pigment production routes ate in commercial use. In the sulfate process, the ore is dissolved in sulfuric acid, the solution is hydrolyzed to precipitate a microcrystalline titanium dioxide, which in turn is grown by a process of calcination at temperatures of ca 900—1000°C. In the chloride process, titanium tetrachloride, formed by chlorinating the ore, is purified by distillation and is then oxidized at ca 1400—1600°C to form crystals of the required size. In both cases, the taw products are finished by coating with a layer of hydrous oxides, typically a mixture of siUca, alumina, etc. 

In the initial thiocyanate-complex Hquid—Hquid extraction process (42,43), the thiocyanate complexes of hafnium and zirconium were extracted with ether from a dilute sulfuric acid solution of zirconium and hafnium to obtain hafnium. This process was modified in 1949—1950 by an Oak Ridge team and is stiH used in the United States. A solution of thiocyanic acid in methyl isobutyl ketone (MIBK) is used to extract hafnium preferentially from a concentrated zirconium—hafnium oxide chloride solution which also contains thiocyanic acid. The separated metals are recovered by precipitation as basic zirconium sulfate and hydrous hafnium oxide, respectively, and calcined to the oxide (44,45). This process is used by Teledyne Wah Chang Albany Corporation and Western Zirconium Division of Westinghouse, and was used by Carbomndum Metals Company, Reactive Metals Inc., AMAX Specialty Metals, Toyo Zirconium in Japan, and Pechiney Ugine Kuhlmann in France. 

The cymidiu sulphouic acid is then diazotised in the usual manner by treating with sodium nitrite in acid solution and the diazo body reduced with alkaline tin chloride solution, or with formic acid and powdered copper, or with other relatively gentle reducing agents. The 3 or 5 cymidin sulphonic acid gives by the above process one and the same cymene sulphonic acid, viz., l-methyl-3-sulphonic-4-isopropyl benzene. 

A mixture of 10.3 g of thiophene-20 -methylacetic acid [prepared by process of Bercot-Vat-teroni, et al.. Bull. Soc. Chim. (1961) pp. 1820-211, 11.10 g of benzoyl chloride and a suspension of 23.73 g of aluminum chloride in 110 cc of chloroform was allowed to stand for 15 minutes and was then poured into a mixture of ice and hydrochloric acid. The chloroform phase was extracted with a 10% aqueous potassium carbonate solution and the aqueous alkaline phase was acidified with N hydrochloric acid and was then extracted with ether. The ether was evaporated off and the residue was crystallized from carbon tetrachloride to obtain a 54% yield of 5-benzoyl-thiophene-20 -methylacetic acid melting at 83°C to 85°C. The... 

The process can also be carried out without solvent )methylene chloride by adding a slight excess of aluminum chloride powder to a solution of one mol of dichloroanisole and one mol of acid chloride. 

Polymerization reactions can occur in bulk (without solvent), in solution, in emulsion, in suspension, or in a gas-phase process. Interfacial polymerization is also used with reactive monomers, such as acid chlorides. 

Chemical reduction is used extensively nowadays for the deposition of nickel or copper as the first stage in the electroplating of plastics. The most widely used plastic as a basis for electroplating is acrylonitrile-butadiene-styrene co-polymer (ABS). Immersion of the plastic in a chromic acid-sulphuric acid mixture causes the butadiene particles to be attacked and oxidised, whilst making the material hydrophilic at the same time. The activation process which follows is necessary to enable the subsequent electroless nickel or copper to be deposited, since this will only take place in the presence of certain catalytic metals (especially silver and palladium), which are adsorbed on to the surface of the plastic. The adsorbed metallic film is produced by a prior immersion in a stannous chloride solution, which reduces the palladium or silver ions to the metallic state. The solutions mostly employed are acid palladium chloride or ammoniacal silver nitrate. The etched plastic can also be immersed first in acidified palladium chloride and then in an alkylamine borane, which likewise form metallic palladium catalytic nuclei. Colloidal copper catalysts are of some interest, as they are cheaper and are also claimed to promote better coverage of electroless copper. 

Acid chlorides are very reactive and have as a condensation product hydrochloric acid.4,7 9 This hydrochloric acid can form an amine salt with unreacted amine groups, which should be avoided. To prevent this happening, acid binders, which are more reactive than the amines, are added. Polyamidation can be earned out using a solution and with an interfacial method. With the interfacial method one has the choice between a stirred and an unstirred process. In an unstirred process, the polymerization is at the interface and a rope can be drawn from the interface,... 

Polylactides, 18 Poly lactones, 18, 43 Poly(L-lactic acid) (PLLA), 22, 41, 42 preparation of, 99-100 Polymer age, 1 Polymer architecture, 6-9 Polymer chains, nonmesogenic units in, 52 Polymer Chemistry (Stevens), 5 Polymeric chiral catalysts, 473-474 Polymeric materials, history of, 1-2 Polymeric MDI (PMDI), 201, 210, 238 Polymerizations. See also Copolymerization Depolymerization Polyesterification Polymers Prepolymerization Repolymerization Ring-opening polymerization Solid-state polymerization Solution polymerization Solvent-free polymerization Step-grown polymerization processes Vapor-phase deposition polymerization acid chloride, 155-157 ADMET, 4, 10, 431-461 anionic, 149, 174, 177-178 batch, 167 bulk, 166, 331 chain-growth, 4 continuous, 167, 548 coupling, 467 Friedel-Crafts, 332-334 Hoechst, 548 hydrolytic, 150-153 influence of water content on, 151-152, 154... 

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